Copper nitrene complexes are highly reactive species and are known as intermediates in the copper catalyzed C-H amination. In this study, three novel copper tosyl nitrene complexes were synthesized at low temperatures, stabilized with heteroscorpionate ligands of the bis(pyrazolyl)methane family. The copper nitrenes were obtained by the reaction of a copper(i) acetonitrile complex with SPhINTs in dichloromethane. https://www.selleckchem.com/products/Menadione.html We show that the ligand design has a major influence on the catalytic activity and the thermal stability of the copper nitrene complex. Not only the choice of the third N donor, but also the substituent in the 5-position of the pyrazolyl moiety, have an impact on the stability. Furthermore, the novel copper nitrene complexes were used for catalytic aziridination of styrenes and C-H amination reactions of aromatic and aliphatic substrates under mild reaction conditions. Even challenging substrates like benzene and cyclohexane were aminated with good yields. The copper nitrene complexes were characterized using UV/Vis spectroscopy, low temperature Evans NMR spectroscopy, density functional theory, domain-based local pair natural orbital coupled cluster calculations (DLPNO-CCSD(T)) and cryo-UHR mass spectrometry.Psychoactive natural products play an integral role in the modern world. The tremendous structural complexity displayed by such molecules confers diverse biological activities of significant medicinal value and sociocultural impact. Accordingly, in the last two centuries, immense effort has been devoted towards establishing how plants, animals, and fungi synthesize complex natural products from simple metabolic precursors. The recent explosion of genomics data and molecular biology tools has enabled the identification of genes encoding proteins that catalyze individual biosynthetic steps. Once fully elucidated, the "biosynthetic pathways" are often comparable to organic syntheses in elegance and yield. Additionally, the discovery of biosynthetic enzymes provides powerful catalysts which may be repurposed for synthetic biology applications, or implemented with chemoenzymatic synthetic approaches. In this review, we discuss the progress that has been made toward biosynthetic pathway elucidation amongst four classes of psychoactive natural products hallucinogens, stimulants, cannabinoids, and opioids. Compounds of diverse biosynthetic origin - terpene, amino acid, polyketide - are identified, and notable mechanisms of key scaffold transforming steps are highlighted. We also provide a description of subsequent applications of the biosynthetic machinery, with an emphasis placed on the synthetic biology and metabolic engineering strategies enabling heterologous production.Cholinium amino acid-based (Ch-AA) biocompatible ionic liquids (bio-ILs) are synthesized from renewable components and are efficiently used for biomass processing. However, their microscopic structural features that lead to their application as biomass solvents remain undetermined. Herein, we use atomistic simulations to investigate the structures of six different Ch-AA bio-ILs up to the nanometer length scale and demonstrate that, depending on the anion side chain structure, the respective IL exhibits structural ordering at different length scales. All the six Ch-AA bio-ILs investigated here show a generic feature of having a strong hydrogen bonding network between the hydroxyl group of the cholinium cation and the carboxyl group of the amino acid anions. We illustrate that each of these bio-ILs also displays a unique feature. Distinctive intermediate range structural ordering leads to heterogeneity in methioninate- and phenylalaninate-based ILs caused by the anion side chain segregation. Intermediate range ordering is not observed in glutaminate- and glutamate-based ILs because significant anion side chain and backbone interactions hinder the formation of side chain clusters. Interestingly, for the cysteinate-based IL, the side chains do not interact with the backbones and the intermediate range ordering is not observed because of a shorter anionic side chain.Perfluorocarbon emulsion droplets are interesting colloidal systems with applications, ranging from diagnostics and theranostics to drug delivery, due to their controllable phase transition into microbubbles via heat application or acoustic droplet vapourisation. This work highlights the application of small- and ultra-small-angle neutron scattering (SANS and USANS, respectively), in combination with contrast variation techniques, in observing the in situ phase transition of polydopamine-stabilised perfluorohexane (PDA/PFH) emulsion droplets into microbubbles during heating. Results show peak USANS intensities at temperatures around 90 °C, which indicates that the phase transition of PDA/PFH emulsion droplets occurs at significantly higher temperatures than the bulk boiling point of pure liquid PFH (56 °C). Analysis and model fitting of the SANS and USANS data allowed us to estimate droplet sizes and interfacial properties at different temperatures (20 °C, 90 °C, and 20 °C after cooling), giving valuable insights about the transformation of these polydisperse emulsion droplet systems.To predict barrier heights at low temperatures, it is not enough to employ highly accurate electronic structure methods. We discuss the influence of quantum tunnelling on the comparison of experimental and theoretical activation parameters (Ea, ΔH‡, ΔG‡, or ΔS‡), since the slope-based experimental techniques to obtain them completely neglect the tunnelling component. The intramolecular degenerate rearrangement of four fluxional molecules (bullvalene, barbaralane, semibullvalene, and norbornadienylidene) were considered, systems that cover the range between fast deep tunneling and small but significant shallow tunnelling correction. The barriers were computed with the composite W3lite-F12 method at the CCSDT(Q)/CBS level, and the tunnelling contribution with small curvature tunnelling. While at room temperature the effect is small (?1 kJ mol-1), at low temperatures it can be considerable (in the order of tens of kJ mol-1 at ?80 K).